Method for purification of as-produced single-wall carbon nanotubes

ABSTRACT

This invention relates generally to a single-wall carbon nanotube (SWNT) purification process and more particularly to a purification process that comprises heating the SWNT-containing felt under oxidizing conditions to remove the amorphous carbon deposits and other contaminating materials. In a preferred mode of this purification procedure, the felt is heated in an aqueous solution of an inorganic oxidant, such as nitric acid, a mixture of hydrogen peroxide and sulfuric acid, or a potassium permanganate. Preferably, SWNT-containing felts are refluxed in an aqueous solution of an oxidizing acid at a concentration high enough to etch away amorphous carbon deposits within a practical time frame, but not so high that the single-wall carbon nanotube material will be etched to a significant degree. When material having a high proportion of SWNT is purified, the preparation produced will be enriched in single-wall nanotubes, so that the SWNT are substantially free of other material.

RELATED APPLICATIONS

This application is a division of prior application Ser. No. 10/000,746,filed on Nov. 30, 2001, which is a continuation of prior applicationSer. No. 09/242,040 filed on Sep. 13, 1999 now abandoned, which is the35 U.S.C. § 371 national application of International Application NumberPCT/US97/13896 filed on Aug. 8, 1997, which designated the UnitedStates, claiming priority to provisional U.S. patent application Ser.No. 60/023,732 filed on Aug. 8, 1996. Each of the foregoing applicationsis commonly assigned to the assignee of the present invention and ishereby incorporated herein by reference in its entirety.

This application discloses subject matter related to the subject matterof U.S. patent application Ser. No. 09/380,545, filed on Sep. 3, 1999 inthe name of Richard E. Smalley et al., entitled “Carbon Fibers FormedFrom Single-Wall Carbon Nanotubes,” which application is commonlyassigned to the assignee of the present invention and herebyincorporated herein by reference in its entirety.

TECHNICAL FIELD OF THE INVENTION

This invention relates generally to the field of macroscopicallymanipulable nanoscale devices that permit information to be provided toor obtained form a nanoscale environment, and more particularly to theuse of nanotubes attached to macroscale mounting members as nanoscaleprobes, fabricators and manipulators.

BACKGROUND OF THE INVENTION

The development of mechanical, electrical, chemical and biologicaldevices and systems that include or comprise nanoscale components,sometimes termed nanotechnology, has been slowed by the unavailabilityof or limitations inherent in devices that enable sensing, measuring,analyzing, and modifying objects with nanometer resolution and sensing,measuring, analyzing, moving, manipulating, fabricating and modifyingobjects with nanometer dimensions.

One class of devices that have found some use in nanotechnologyapplications are proximity probes of various types including those usedin scanning tunneling microscopes (STM), atomic force microscopes (AFM)and magnetic force microscopes (MFM). While good progress has been madein controlling the position of the macroscopic probe to sub-angstromaccuracy and in designing sensitive detection schemes, the tip designsto date have a number of problems.

One such problem arises from changes in the properties of the tip asatoms move about on the tip, or as the tip acquires an atom or moleculefrom the object being image Another difficulty with existing probemicroscope tips is that they typically are pyramidal in shape, and thatthey are not able to penetrate into small “hole” on the object beingimaged, and they may give false image information around sharp verticaldiscontinuities (e.g., steps) in the object being imaged, because theactive portion of the “tip” may shift from the bottom atom to an atom onthe tip's side. Moreover, conducting conventional probe microscope tipshave never been successfully covered with an insulating material so thatthe only electrically-active element is the point of the tip itself.

Conventional probe microscope tips also are very rigid in comparison tomany of the objects to be examined, and with “soft” samples (e.g.,biomolecules like DNA) conventional AFM tips misrepresent the thicknessof the object imaged, because that object is literally compressed by theaction of the tip.

Thus, there is a need for macroscopically manipulable nanoscale devicesfor observing, fabricating or otherwise manipulating individual objectsin a nanoscale environment that address the foregoing and otherdisadvantages of the prior art.

SUMMARY OF THE INVENTION

The present invention employs geometrically-regular molecular nanotubes(such as those made of carbon) to fabricate devices that enableinteraction between macroscopic systems and individual objects havingnanometer dimensions. These devices may comprise one or more individualnanotubes, and/or an assembly of nanotubes affixed to a suitablemacroscopically manipulable mounting element whereby the device permitsmacroscale information to be provided to or obtained from a nanoscaleenvironment.

Individual nanotubes or bundles of nanotubes can be recovered from amaterial (such as the carbon nanotube “ropes”) grown by proceduresdescribed herein. Assemblies of nanotubes can be fabricated by physicalmanipulation of nanotube-containing material, or by self-assembly ofgroups of nanotubes, or by chemical physical, or biological behavior ofmoieties attached to the ends or to the sides of the nanotubes orbundles of nanotubes. Individual nanotubes or assemblies of nanotubescan be grown to achieve specific characteristics by methods describedherein.

More particularly, the devices of the present invention can compriseprobes with tips comprising one or more molecular nanotubes. Whenattached to an appropriate motion transducer (piezoelectric, magneticetc.) the probe is capable of sensing, measuring, analyzing, andmodifying objects with nanometer resolution and sensing, measuring,analyzing, moving, manipulating, and modifying objects with nanometerdimensions.

A method for making such devices is disclosed, which includes the stepsof (1) providing a nanotube-containing material; (2) preparing ananotube assembly comprising at least one nanotube from thenanotube-containing material; and, (3) attaching the nanotube assemblyto a macroscopically manipulably mounting element.

The nanoscale devices according to the present invention provide strong,reliably mounted probe tips and other nanoscale fabricators andmanipulators, that are gentle, hard to damage, even upon “crashing” intothe working surface, that can be easily made electrically conductive,that can present a uniform diameter and precisely known atomicconfiguration, including precisely located derivitization with chemicalmoieties.

The devices of the present invention have a number of advantages overconventional microscopy probes (e.g. STM and AFM). A probe tipconsisting of a single molecular nanotube or a few such tubes has theadvantage that all its constituent atoms are covalently bonded in placeand are unlikely to move, even under extreme stress, such as thatoccurring when the tip “crashes” into the object being imaged. Moreover,the known, stable geometry of molecular nanotube tips allows one to moreaccurately interpret the data acquired by probe microscopes using suchtips. In addition, molecular nanotubes are very compliant, buckling in agentle, predictable, and controllable fashion under forces that aresmall enough to avoid substantial deformation to delicate sampleobjects. Unlike currently used pyramidal probe tips, molecular nanotubesare very long with respect to their diameter, and can therefore reliablyimage the bottom areas of holes and trenches in the items being imaged.

Electrically conducting nanotube tips can be coated with an insulatingmaterial to achieve localized electrical activity at the end of theprobe element This geometry facilitates probing of electrochemical andbiological environments.

Molecular nanoprobe elements have remarkably different chemical activityat their ends because the atomic configuration on the ends differsfundamentally from that of the sides. Consequently, one can selectivelybond specific molecules to the tip end. This site specific bondingenables chemically-sensitive probe microscopy, and a form of surfacemodification in which some superficial atoms or molecules of the objectbeing imaged react chemically with the probe tip or species attached orbonded to it. This delicate chemistry enables a form of surfacemodification that is not possible with conventional tips. This surfacemodification can serve as a direct manipulation technique fornanometer-scale fabrication, or as a method of lithography in which a“resist” is exposed by the chemical or electrochemical action of thetip.

BRIEF DESCRIPTION OF THE DRAWINGS

For a more complete understanding of the present invention, the objectsand advantages thereof, reference is now made to the followingdescriptions taken in connection with the accompanying drawings inwhich:

FIGS. 1 a–e illustrate various embodiments of probe tips according tothe present invention.

FIGS. 2 a–c show a typical nanotube probe according to one embodiment ofthe invention.

FIG. 3 a shows the frequency dependency of the amplitude of a SFM with ananotube tip engaged in tapping mode.

FIG. 3 b shows the result of a direct numerical simulation using abuckling force equation.

FIG. 3 c shows how the amplitude of an SFM cantilever (driven at afrequency of 253.8 kHz) changes as it engages a surface.

FIGS. 4 a–d illustrates the probing capabilities of nanotube tips.

FIGS. 5 a–c show the frequency dependency of a cantilever having ananotube probe immersed in water.

FIG. 6 shows an example of atomic-scale resolution STM using a carbonnanotube to image the charge density waves on a freshly cleaved 1T-TaS2surface.

FIG. 7A is a TEM/SEM/Raman spec of purified SWNTs useful in the practiceof the present invention.

FIG. 7B is a TEM/SEM/Raman spec of purified SWNTs useful in the practiceof the present invention.

FIG. 7C is a TEM/SEM/Raman spec of purified SWNTs useful in the practiceof the present invention.

FIG. 8 is a schematic representation of a portion of an homogeneous SWNTmolecular array useful in the practice of the present invention.

FIG. 9 is a schematic representation of an heterogeneous SWNT moleculararray useful in the practice of to the present invention.

FIG. 10 is a schematic representation of the growth chamber of the fiberapparatus useful in the practice of to the present invention.

FIG. 11 is a schematic representation of the pressure equalization andcollection zone of the fiber apparatus useful in the practice of to thepresent invention.

FIG. 12 is a composite array useful in the practice of the presentinvention.

FIG. 13 is a composite array useful in the practice of the presentinvention.

DETAILED DESCRIPTION OF THE INVENTION

The preferred embodiment of the present invention and its advantages arebest understood by referring to FIGS. 1 through 13 of the drawings, likenumerals being used for like and corresponding parts of the variousdrawings.

Macroscopically Manipulable Nanoscale Devices

Broadly, the macroscopically manipulable nanoscale devices of thepresent invention comprise a nanotube assembly attached to a mountingelement that permits macroscopic manipulation or observation In apreferred form this device comprises a nanotube probe tip assembly madeup of one or more single-wall and/or multi-wall nanotubes. This assemblyis connected to a mounting element at one end, with the other end beingfree and capable of coming into direct contact or near proxy to theobject being sensed, measured, analyzed, moved, manipulated, and/ormodified. The free “sensing end” has a transverse dimension in thenanometer range. The “sensing end” interacts with objects being sensed,measured, analyzed, moved, manipulated, and/or modified by means whichare (either individually or in combination) physical, electrical,chemical, electromagnetic, or biological. These interactions produceforces, electrical currents, or chemical compounds which revealinformation about the object and/or modify that object in some way.

Mounting Element

The mounting element facilitates the transduction of information betweenthe macroscopic and nanoscopic worlds. The mounting element supports andmoves the probe, and may provide electrical connections to the probe. Inaddition, the mounting element may serve as a transducer that converts aphysical, chemical, electrical, mechanical, or optical response of theprobe itself to another form that is more readily detectable byinstrumentation known to those skilled in the art of probe microscopy.The mounting element also serves to enable the probe's motion and tofacilitate its action in the sensing, measuring, analyzing, moving,manipulating, and modifying other objects.

For many analytical applications, the currently employed mountingsystems can be employed in carrying out the present invention. In thisregard, the cantilever or probe tip of various known proximity probessuch as STM, AFM and MFM devices can save as the mounting element of thepresent invention. These devices typically provide for observation of oractivation by macroscopically manipulable forces, using sensing methodsthat typically measure the deflection of the mounting element (e.g.,cantilever) by electronic (e.g., tunneling current), optical (e.g.,optical interferometry or beam deflection, or electro mechanical (e.g.,piezoelectric) elements. For the structure and operation of suchconventional mounting elements, reference can be made to the following,all of which are hereby incorporated by reference in their entirety:

Marcus et al. U.S. Pat. No. 5,475,318 Beha et al. U.S. Pat. No.4,918,309 Jain et al. U.S. Pat. No. 5,566,987 Burnham et al. U.S. Pat.No. 5,193,383

In the devices described in these references and others of similarfission and structure, the present invention contemplates replacing oraugmenting the probe tip, or surface interaction element, with ananotube assembly as described below.

Nanotube Assembly

The nanotube assembly of the present invention can be formed from anygeometrically regular molecular nanotubes, and is preferably preparedfrom isolated, purified carbon nanotubes produced by any of the methodsdescribed herein. The carbon nanotube can be multi-wall or single-wall,with single-wall carbon nanotubes being preferred. The single-wallcarbon nanotube can be of the metallic type, i.e. arm chair or (n,n) inconfiguration or of the insulating type, i.e. (m,n) in configuration.For applications requiring electrical conductivity, the most preferredare (10,10) SWNTs. The carbon nanotubes may be substituted, i.e., havelattice atoms other than C (e.g. BN systems) or externally derivitizedby the addition of one or more chemical moieties at either a sidelocation, an end location, or combinations. The carbon nanotubes mayalso be endohedrally modified by including one or more internal speciesinside the structure. Suitable endohedral species include metals (e.g.Ni, Co, Yb), ions, small molecules and fullerenes. Endohedral speciesmay have magnetic properties (i.e. ferromagnetic, paramagnetic),electrochemical properties, optical properties, or other suitableproperties.

The structure of the nanotube assembly can vary depending on the purposefor which the device is used. In many cases, a single nanotube willserve as the nanotube assembly. Referring to FIG. 1 a, such an assemblyis shown. Nanotube assembly 100 consists of a mounting element 104 witha single nanotube 102 attached thereto. Small bundles of generallyparallel and coterminating nanotubes containing from about 2–100nanotubes, preferably about 2 to about 20 nanotubes and most preferablyabout 5 to about 10 nanotubes, can also be employed. (See FIG. 1 b).This assembly 120 consists of a bundle of nanotubes 122. This bundle 122can be held together by van der Waals forces or otherwise boundtogether.

In one preferred embodiment shown in FIG. 1 c, a bundle of nanotubes 142forming the nanotube assembly 140 includes at least one nanotube 144that extends beyond the end of the other nanotubes in the bundle. Thisextension can result from employing at least one longer nanotube orbonding an extension length to the end of the bundle (i.e. to one of thebundle length nanotubes). Also, as shown in FIG. 1 d and describedbelow, the nanotube assembly 160 may be coated (preferably afterattachment to the mounting element) with a suitable material 164.

The diameter of the nanotube assembly can be uniform along its length(as in the embodiment of FIG. 1( a) and 1(b) or non uniform along itslength (as in the embodiments of FIG. 1( c) and (d)). Even in the latterforms it is preferred that the tip section of FIG. 1( c) and (d)respectively is of uniform diameter. Useful diameters can range from afew nm (for single tubes) up to about 100 nm for ropes or bundles.Preferred are bundles having diameters of about 2 nm to about 50 nm, andmost preferred are diameters of about 5 nm to about 20 nm.

The total length of the nanotube assembly can be from about 1 to 100times its diameter, preferably greater than 20 times its diameter. Ingeneral, lengths of from about 50 to about 10,000 nm are employed,depending on the nature of the device and its intended environment ofoperation. For probes (e.g. STM, AFM) the nanotube assembly should befrom about 50 nm to 5000 nm in length with about 300 nm to about 500 nmbeing preferred. For structures of the type shown in FIG. 1( c) thesingle nanotube tip portion can extend for up to ½ or more of the lengthof the total assembly. For example, a 550 nm long tip of the type shownin FIG. 1( c) has a body section 142 of about 300 nm and a tip section144 of about 250 nm.

Method of Attaching a Nanotube Assembly to a Mounting Element

In another embodiment, a method for attaching a nanotube assembly (whichcan include a single nanotube or a bundle, e.g., a rope of nanotubes) toa mounting element is provided. Fundamental to the mounting process isthe surprising realization that the nanotubes, which in two dimensionsare substantially smaller than the wavelength of visible light (evenwhen several run alongside each other in a thicker bundle), maynevertheless be adequately perceived with an optical microscope topermit their observation and mounting. This observability under visibleillumination is possible because, for the component of light which ispolarized along the length of the nanotube (in which direction thenanotubes are longer than the wavelength of visible light), where thiscomponent has adequate intensity and the scattering from other objectsis minimized to permit contrast, the nanotubes scatter light withsufficient efficiency to be rendered observable.

In the case of through the objective lens illumination utilizingunpolarized white light, the source must be made so intense that evenwith high quality anti-reflection coated optics, reflections fromoptical component surfaces and the scatting of light from imperfectionsin the optical components renders the contrast too poor to permitobservation of individual nanotubes or thin bundles. This limitation islargely circumvented by application of the dark field technique;however, even with the advantages that this provides, confirmation thata very thin sample, which appears to the dark adapted eye as the barestvisible ghost of an image, requires a sensitive camera capable ofintegrating the image (operationally, for quick assessment an electronicdevice such as a CCD camera, rather than film is desirable).Alternatively, a thin laser beam, polarized along the direction of thenanotube, is passed through an off axis portion of the objective lenswhere the back reflections from optical components are directed out ofthe field of view and imperfections in the components are avoided (asindicated by minimizing the degree of extraneous field illumination asthe beam is moved around to different portions of the objective).Alternatively, light (white or laser) is trained on the sample from aside perpendicular to the axis of the nanotube such that lightscattering off the nanotube enters the microscope objective. In allthese cases the visibility of the sample is greatly enhanced when theorientation of the nanotube, relative to the propagation direction ofthe illumination and the optic axis of the microscope are arranged as ifa mirror resides in the plane of the nanotube, oriented such as tomaximize the specular reflection of the source into the field of view ofthe microscope

The first step in the method of this invention is to provide ananotube-containing material. As discussed below, there are severaltechniques for preparing these materials. The next step in the processinvolves preparation of the nanotube assembly. For assemblies made ofsingle nanotubes or bundles of nanotubes this step may compriseseparating an individual nanotube or bundle form a material containingthese forms. For example, for raw arc grown boule, a small piece ofboule material can be ripped from the as grown deposit and attached toits mount using double-sided tape. For oxygen purified material, a smallpiece may similarly be ripped from the purified boule. Individualnanotubes and bundles which stick out from this piece of boule(outliers) are then available for attachment to the mounting device.Generally it is found that such a sample presents few outliers and theyare often too well embedded in the dense piece of boule to permitpulling out. More opportunities are presented if the raw boule materialis ground into roughly 10–100 μm chunks which are then picked up bydouble-sided tape. In another embody the nanotube assembly can comprisecarbon fibers grown from SWNT molecular arrays as described below.Carbon fibers grown using the random growth of carbon fibers from SWNTsas described below, also may be used.

The next step in the method of this invention involves attaching to(mounting) the nanotube assembly to the mounting element. The mountingprocedure requires at minimum two precision XYZ translation stages,stages A and B. These stages must be arranged such that the sharp pointor edge of the mounting element to which the nanotube assembly (singleor bundle) is to be mounted is supported by one of the translationstages in the field of view of the microscope (stage A), while a mass ofnanotubes from which the nanotube sample is to be culled is similarlysupported in the microscope field of view by the second translationstage B. Manual actuators for these stages are adequate for themounting, however, for some applications, additional final samplepreparation steps require the use of electromechanical actuators.

It is found that the number of outliers available for attachment isgreatly enhanced if the surface of the piece of boule has a piece oftape gently touched to it such that nanotubes become embedded in theadhesive layer and the tape is then lifted off in a directionperpendicular to the surface, pulling out a layer of nanotubes tens ofmicrons thick. The tug of war between the nanotubes on either side ofthe boundary layer separating the two newly formed surfaces (one on theremaining piece of boule and the other on the piece of tape) has theeffect of orienting the exposed nanotubes perpendicular to each newsurface thus generating the numerous outliers. In an alternateembodiment, it may be desirable to mount the piece of tape on stage Band then to cull the nanotube sample from this material.

For mounting the nanotube sample onto the mounting device, a selectedoutlier is situated in the field of view of the microscope while theappropriate tip or edge of the mounting device is brought up alongsidethe outlier such that there is appreciable overlap. The mounting deviceor outlier is then translated in such a manner that contact is madebetween the two over the length of the overlap. Attachment of theoutlier to the mounting device tip with sufficient bond strength topermit the nanotube sample to be detached from the mass of nanotubesaffixed on stage B may be effected in several ways.

In a preferred embodiment, the force of attachment is provided by thevan der Waals bonding between the nanotube sample and the surface of themounting device. For X to be sufficiently strong to extra the sample thesurface of the mounting device must have large sections which are smoothand regular on an atomic scale permitting intimate contact between thenanotube sample surface(s) and the device side. A highly graphitizedcarbon fiber (commercially available) is an example of such a device,which being electrically conducting, additionally provides forelectrical connection to the nanotube. The graphitic nature of thesurface in this case makes the total bond strength particularly strongsince the atomic registration between the graphene surface of nanotubesand the graphitic surface of the fiber permits particularly intimatecontact over more atoms per unit area than any other surface.

Once intimate contact between the sample and the mounting device hasbeen made, the mounting device is translated in a direction away fromthe nanotube layer. Often, when the bond strength of the nanotube sampleto the mounting device tip surface exceeds the strength of its bonds toother nanotubes that it contacts on the tape side layer, the nanotubesample is extracted from the layer and now freely attached to themounting device.

For some applications, it is necessary to have the tip of the nanotubesample extend fisher from the point of attachment on the mounting devicethan the typical length of the extracted sample yields. In such cases alonger sample is generated by attaching one nanotube sample and thenrepeating the above procedures with the tip of this sample treated asthe tip of the mounting device. This may be repeated as often as desire.This procedure may also be applied when the nanotube sample consists ofa bundle of nanotubes which end close together but a single nanotube tipsample, of longer single nanotube length, is desired. In that case thelast outlier attached should be very faint and uniform in the intensityof its light scattered indicating it to be a single nanotube.

In another preferred embodiment, the tip of the mounting device to whichthe nanotube sample is to be attached is pretreated with a thin adhesivelayer before contact to the nanotube sample is made. The adhesive can beone which must cure like an epoxy resin in order to form a bond or onewhich remains tacky. An example of the latter is provided by theadhesive layer on the double sided tape which is used to affix thenanotube mass to its mount on stage B. This is particularly convenientbecause the thin adhesive layer can be applied to the tip of themounting device, in situ under microscopic observation, just prior tonanotube sample contact. To accomplish this, the mounting device tip istranslated to a nanotube free region of the tape, where the tip is thendriven a few microns into the adhesive layer and subsequently withdrawn,pulling out with it a thin layer of the adhesive which has coated thetip. Contact with an outlier is now made as above and the nanotubesample similarly extracted. In the case of an adhesive requiring a curethe appropriate conditions (e.g., UV light, heat, hardener etc.) must beprovided to effect the cure prior to attempting to extract the sample.

In this implementation, if electrical connection to the nanotube sampleis required such connection can be guaranteed (despite the use ofinsulating adhesives) by applying the adhesive to only the very tip ofthe mounting device and selecting only the longest outliers to ensurethat there is direct contact between the uncoated, electricallyconducting portion of the mounting device tip (beyond the adhesivecovered portion) and the nanotube sample.

In some applications, the mounted nanotube sample may be subjected tomechanical or environmental stresses which make it desirable to make theattachment to the mounting device more robust. This is accomplished bythe application of a coating over the nanotube sample and mountingdevice tip. While this has been achieved by dipping the assembly in afluid solution of the coating material, it is found that delivery of thecoating material from the vapor phase has several distinct advantages.These include: a) stresses on the sample are minimized during theprocess ensuring that the sample survives, b) the amount of the coatingmaterial applied my be controlled by simple control over the time ofdeposition and is not subject to more difficult to control viscosity andsurface tension parameters encountered using the application of fluidmedia, and c) for some coating materials (in particular, those which donot undergo a liquid phase upon condensing on the sample) it is possibleto obtain a nanometer scale coating thickness which is uniform over thewhole of the nanotube sample.

Coatings applied in this way can include cyanoacrylate, methacrylate(modified and pure, both in two part cure formulation and a UV cureformulation), Parylene2 and polyimide. Other types of coatings that maybe applied from the vapor phase include silicon from the UVdecomposition of silanes in an inert atmosphere as well as silicondioxide from the decomposition of silanes in an oxygen atmosphere.Finally, metals may be coated on the nanotube samples from vapors oforganometallic species (e.g., Fe from Fe(CO)₃).

In some applications, the coating has important utility beyond that ofsecuring the nanotube sample onto the mounting device tip. In the caseof some biological and electrochemical probing applications, it isnecessary that the probe be electrically insulated from its fluidenvironment at all but its very tip. The polymeric coatings mentionedabove each provide a uniform, insulating coating that adds littlethickness to the probe diameter, are ideal for this application. Thepolymer for coatings may include a fluorescent species for renderingnanotubes more visible, e.g., against the background of a cell. In otherapplications (e.g., for field emission sources) it is necessary thatthermal vibrations of the nanotube sample, fixed as it is at only oneend, be minimized. In such cases, the coating thickness may be made aslarge as necessary to adequately stabilize the tip. In both theseinstances, it may be necessary to remove the coating from the last fewhundred nanometers at the tip of the nanotube sample.

If the holder fixing the mounting element with its mounted nanotubesample on stage A and the holder fixing an opposing sharp tippedelectrode on stage B are electrically isolated from the microscope base,and each other, an electrical potential can be applied between thenanotube sample and opposing electrode. A consequence of this is that asstage A is translated so as to bring the nanotube sample tip into theproximity of the electrode tip, the oppositely charged objects attracteach other causing the flexible nanotube sample to bend into alignmentwith the electrode tip. One utility of this involves visibility of theattached sample. It was mentioned above that or thin tipped nanotubesamples (single or thin bundle), the visibility of the sample dependsstrongly on the relative angles between the incident light, the nanotubeaxis, and the microscope optic axis. Thus, in an attempt to mount ananotube sample, if the nanotube is not observed at the tip of themounting device it may in fact be attached there however, at an anglethat does not permit its observation. By allowing the orientation of thenanotube to be modified to an angle allowing it to be observed, thistechnique provides a quick assay of whether or not a sample has beenattached. The opposing electrode can simply be another outlier from thelayer of nanotubes from which mounting is being attempted on stage B.

Probes for Analytical Applications

The molecular nanotubes attached to a mounting element, according to thepresent invention, enable the fabrication of probes for variousanalytical applications on a nanoscale. The probe and its mountingelement essentially provide a transducer for interacting with ananoscale environment. Conventional probe microscopy techniques areenabled and improved by the use of nanotube probe elements of thisinvention.

A molecular nanotube probe element is fundamentally different fromconventional probe microscopy tips in shape, and mechanical, electronic,chemical and electromagnetic properties. These differences permit newmodes of operation of probe microscopes, and new forms of probemicroscopy.

Probes according to the present invention include those useful inimaging, at nanoscale resolution or greater, surfaces and othersubstrates including individual atoms or molecules such as biomolecules.Examples of conventional probe microscopy of this type include scanningtunneling microscopes (STM), atomic force microscopes (AFM), scanningforce microscopes (SFM), magnetic force microscopes (MFM), and magneticresonance force microscopes (MRFM). In this type of probe theconventional tip element can be replaced by the nanotube assembly andexisting mounting systems (e.g. the cantilever or a tip on a cantilever)form the mounting element.

FIG. 1 e shows a typical STM or AFM probe having a cantilever 180 whichhas a conventional tip 182 and a nanotube assembly 184 (in this case asingle nanotube) extending from the tip. The nanotube assembly 184 maybe attached to the tip 182 in the same fashion discussed earlier. Thecantilever 180 can be used as a part of a larger device in the knownmanner. A coating, as described above, may be applied to the probe andthe mounting element.

In a preferred embodiment the mounting devices may be pre-coated with alayer of conductive metal in order to produce a good electrical contactto the nanotube probe.

When used in tapping mode AFM (where the change in amplitude of anoscillating cantilever driven near its resonant frequency is monitoredas the tip taps the surface; the sharp frequency response ofhigh-quality cantilevers make this technique exquisitely sensitive. Acarbon nanotube tip, such as that shown in FIG. 1( c), has the unusualadvantage that it is both stiff below a certain threshold force, but iscompliant above that threshold force. The is no bending of the nanotubeat all when it encounters a surface at near normal incidence until theEuler buckling force, F_(EULER) is exceeded, which is given by theequation:F _(EULER) =n π ² YI/L ²  (1)where n is a parameter determined by the tip mounting, Y is the Young'smodulus, I is the moment of inertia of the tip cross section and L isthe free length of the tip extending beyond the mounting assembly. TheEuler buckling force for tips of the preferred embodiment describedabove is in the one nano-Newton range. Once the Euler bucking force isexceeded, the nanotube will bend easily through large amplitudes withlittle additional force. Euler bucking therefore serves as a kind ofinsurance policy during SFM imaging: the maximum force that can betransmitted to the sample is F_(EULER). In addition, the nanotube tip isextremely gentle when touching an object laterally. The bending motionfor side-directed forces is harmonic with a force constant,k_(n)=3YI/L³. For the nanotube tip of FIG. 1( c), k_(n)=6.3 pN/nm.

The non for reduction in the tapping amplitude in operation is almostentirely elastic. The spring force from the bending nanotube produces ade-excitation of the cantilever oscillation at driving frequencies belowthe critical frequency, ω*. The result is that gentle, reliable AFMimaging may be accomplished in the tapping mode with even extremelystiff high-resonant frequency cantilevers. In contrast to the hardsilicon pyramidal tip which can easily generate impact forces >100 nNper tap which may substantially modify the geometry of “soft” samplessuch as large bio-molecules. The nanotube probe serves as a compliantspring which moderates the impact of each tap on the surface, the peakforce never exceeding F_(EULER).

An example of a typical nanotube probe according to one embodiment ofthe invention is shown in FIGS. 2 a–c. A single nanotube was attached tothe pyramidal tip of a silicon cantilever for scanning force microscopy.The majority of the 5.5 micron length extending beyond the pyramidalsilicon tip was a bundle of 5–10 parallel nanotubes, arranged in van derWaals contact along their length. As evident in the TEM image of FIG. 2c, this bundle narrows down to just a single nanotube 5 nm in diameter,extending alone for the final 250 nm.

The nanotube tip shown in FIGS. 2 a–c was operated in tapping mode SFM.FIG. 3 a shows the frequency dependence of the amplitude of thecantilever as it engaged a freshly cleaved surface of mica in air. Asseen in FIG. 3 c, the tapping amplitude when the cantilever was drivennear its resonant frequency (253.8 kHz) dropped rapidly as soon as thenanotube tip came in contact with the mica surface. The amplitudedropped to near zero when the nanotube hit the surface at the midpointof its oscillation, and then recovered to nearly the full in-airamplitude when the surface was so close that the tip was always incontact, with the nanotube flexing throughout the oscillation. FIG. 3 bshows the result of a direct numerical simulation of this experimentusing the buckling force expression of equation (1). The sharpness ofthe recovery of oscillation amplitude near the critical frequency,{acute over (ω)} 254.2 kHz is a sensitive function of the bucklingforce.

Referring to FIGS. 4 a–d, which show that long, narrow nanotube tips canreach into deep trenches previously inaccessible to high resolutionscanning probes. As is evident in FIG. 4 a, the normal pyramidal tip issimply too wide to reach the bottom of a 0.4 m wide 0.8 m deep trench,while the nanotube permits the roughness of the silicon surface at thebottom to be imaged easily. Also as shown in FIG. 4 d, it is possibleusing a voltage pulse on the nanotube to deposit a 40 nm dot of carbonat the bottom of the trench, and then to go back and image the dot. Dueto the “spring loading” of the nanotube bundle to the cantilever and thehigh strength and flexibility of the carbon nanotubes, SFM imaging oftortuous structures such as the trenches shown in FIGS. 4 a–d can bedone without fear of damage either to the nanotube tip or the trenchstructure itself.

One of the principal limits in SFM imaging in air has been that atnormal humidity the surface is covered with layer of water, and thecapillary adhesion forces produced when the tip makes contact aretypically 10–100 nN. As a result one is forced to use high forceconstant cantilevers oscillating with substantial amplitude to insurethat the tip does not get caught by the surface. Due to the smalldiameter of the nanotube, the capillary adhesion force of nanotube tipsis generally reduced to <5 nN and often as low as 0.05 nN, permittingtapping mode imaging with cantilevers having force constants as small as0.01 N/m at a peak-to-peak amplitude of 10 nm.

In order to get away entirely from the capillary adhesion force it isnow conventional to place the entire AFM transducer assembly under somefluid—normally water. However, now that the cantilever must oscillate inwater it is no longer possible to operate at high frequency and high Q.A nanotube tip similar to that of FIG. 2 a, was immersed under thesurface of water, thus leaving the cantilever free to oscillate in air.FIG. 5 a shows that the frequency dependence of the cantileveroscillation is only slightly affected when the lower 0.7 micrometerlength of the nanotube is immersed in water within the trend Also shownis the amplitude of the cantilever oscillation as a function of distancefrom the meniscus at the top of the trench. FIGS. 5 b and c show theamplitude change upon dipping a nanotube probe into the flooded trench.The first contact with the water surface occurred at z=0. The nanotubetip encountered the bottom of the trench at z=−820 nm. The trace in FIG.5 b was done at the resonant frequency of the cantilever oscillating inair (234.74 kHz), and the trace in FIG. 5 c was done at 235.65 kHz,where the oscillation amplitude is seen to substantially increase whenthe tip of the nanotube extends under the water surface.

Since the nanotubes can be electrically conductive, they may be used asprobes for scanning tunneling microscopy, STM and in various scanningelectrochemical modes as well. FIG. 6 shows an example of atomic-scaleresolution STM using a carbon nanotube to image the charge density waveson a freshly cleaved 1T-TaS₂ surface.

The nanotube probe assemblies of this invention also enable theelicitation of other information from and/or about nanoscale objects orat nanoscale resolution such as conventional friction force microscopy(FFM) which measures the atomic scale friction of a surface by observingthe transverse deflection of a cantilever mounted probe tip. Thecompliance of a nanotube probe of the present invention above the Eulerthreshold as described above, provides for a totally new method ofelastic force microscopy (EFM). By calibration of the Euler bucklingforce for an individual probe tip, and making appropriate AFMmeasurements with that tip, one can obtain direct information about theelastic properties of the object being imaged.

Probe tips may also be used to perform nanoscale surface topographymeasurement. The vertical and horizontal motions of the probe assemblycan be calibrated by measurement of surfaces having known geometries(e.g., pyrolytic graphite with surface steps). A thusly-calibrated probeassembly can provide precise measurement of the topography of surfacesand fabricated elements such as vias and trenches on integrated-circuitelements in silicon, gallium arsenide, and other electronic substrates.

A number of other new probe microscopy techniques for obtaininginformation at nanoscale resolution or about/from nanoscale objects isenabled by the present invention. For example, mechanical resonancemicroscopy (MRM) can be facilitated by mechanical resonances in thenanotube probe element itself. These resonances may be utilized as ameans of transduction of information about the object being sensed ormodified. Such resonances, as will be known by one skilled in the art,can be sensed by optical, piezoelectric, magnetic and/or electronicmeans. Interaction of a mechanically resonant probe tip with otherobjects may be facilitated by derivitization of the probe tip orinclusion of an endohedral species (e.g., one which is optically- ormagnetically-active) at or near the probe tip. Mechanically resonanttips can be employed to deliver or receive electronic or optical signalsbetween electronic or optical circuits.

Another novel method for transducing information about an object beingsensed or modified is based on the property of the nanotube probeassemblies of this invention to act as sensitive “antenna” forelectromagnetic radiation (particularly at optical frequencies). Theprobe's response to electromagnetic radiation may be sensed byscattering of that radiation by the probe itself detection andmeasurement of radio frequency (RF) or microwave frequency (MW) currentspassing through the probe as it and the object being sensed interacttogether in a nonlinear way with electromagnetic radiation of two ormore frequencies. Moreover, via its interaction with electromagneticfields of specified frequencies, the probe may excite electronic,atomic, molecular or condensed-matter states in the object beingexamined, and the transduction of information about that object mayoccur by observation of the manifestations of these states.

In another embodiment, the devices of the present invention canfacilitate the storing of information in nanoscale objects and theretrieval of the stored information from those objects by vie of theelectronic, mechanical, physical an/or optical response of the molecularnanotube probe elements in interaction with said objects.

Of particular interest is the use of molecular nanotube probe devicesaccording to the present invention in biological systems. In one suchapplication, DNA sequence can be preformed, for example, by AFM imagingof DNA molecules with a nanotube probe element that, due to its physicaland chemical properties, permits the recognition of individual bases inthe molecule. In another biological application, the probes may also beused as nanelectrodes for electrochemical studies of living cells. Inanother embodiment an ion-selective nanotube may be fabricated from aopen nanotube filled with water and covered with a selective membrane(e.g., ion-exchange resin, or even a biological membrane). Thisnanoelectrode can monitor specific cytoplasmic ions with a spatialresolution far superior to those presently available. In a preferredembodiment, a calcium-specific nanoelectrode may be used to provide highspatial and temporal resolution in the measurement of changes in thecytosolic calcium concentrations, often the response to stimuli, invarious types of cells.

Derivatized probes can serve as sensors or sensor arrays that effectselective binding to substrates. Devices such as these can be employedfor rapid molecular-level screening assays for pharmaceuticals and otherbioactive materials.

Probes as Nanoactuators

The molecular nanotube probe elements of the present invention can alsobe employed to effect manipulation or modification of objects on ananoscale to facilitate the fabrication of nanotechnology devices orelements. In general, these techniques employ some form of tip/sampleinteraction to effect this manipulation or modification. Thisinteraction can be direct physical interaction (e.g., to push, pull ordrag atoms, molecules, or small objects to a specified location).Indirect interaction can be supplied through forces such as repulsion orattraction (atomic force or magnetic force). Emission from the nanotubetip (e.g. electrons, photons, magnetic forces and the like) may alsoeffect the interaction by electromechanical or chemical means, asdescribed more fully below.

Probe-like assemblies of molecular nanotubes can be used with or withoutderivatives as tools to effect material handling and fabrication ofnanoscale devices. Examples of nanostructure fabrication are given inU.S. Pat. No. 5,126,574 to Gallagher and in U.S. Pat. No. 5,521,390 toSato et al., both incorporated by reference in their entireties.

The nanoscale device of the present invention also may be used fornanolithography. A nanotube may be mounted on the tip of a device, suchas a STM. In operation the STM tip then produces a highly-localized beamof electrons which may be used to expose an electron-sensitive resist orto directly modify the surface upon which it impinges. Such surfacemodification or exposure of a resist is useful in fabrication ofelectronic and other devices having dimensions in the nanometer range,which are smaller than those now available.

Addition of selected chemical species to the end of the nanotube probetip permits the probe tip to participate in specific chemical orelectrochemical processes. The tip can then act as an agent for chemicalmodification of a surface or object on a nanometer scale. The pattern ofthis chemical modification is controlled by the collective action of theprobe tip and its mounting mechanism.

The ability to precisely and reproducibly covalently bond a chemicalmoiety at the tip of the preferred carbon nanotube probe structurefacilitates another form of chemical interaction with a surface thatresults in a powerful nanofabrication technique. The (10,10) armchaircarbon nanotube has, at its tip, a single pentagon with reactive sitesfor addition chemistry in its radiating double bonds. By dipping a probe(or array of probes) into a reactive medium, preferably a solution, itis possible to add a chemical moiety that acts as a catalyst to thenanotube tip. This moiety can be a catalyst per se (e.g. an enzyme) or alinking moiety (e.g., a co-enzyme) that has an affinity for a secondmoiety that is the catalytic moiety, which can be added in a secondstep. The preferred system only creates a chemical reaction product whenthe catalyst containing probe tip, the substrate surface, and areagent(s) flowing over the substrate come into contact. An elementformed by the catalyzed reaction product can be positioned discreetly orcontinuously by intermittent or continuous contact of the probe tip withthe surface of a substrate. A complex nanostructure can be built up byperforming the above-described probe/surface reaction step sequentiallywith different probe catalyst/reagent systems to deposit differentpattern elements of the device being nanofabricated. Confirmation thatthe reaction product elements have in fact been formed on the surfacecan be accomplished by employing a phosphorescent marker that is formedupon completion of the reaction. This system can produce a compositestore with extremely fine lines as well as elements of differing shapeand composition. The reaction products forming the pattern(s) or devicestructure can be biomolecules which facilitate the fabrication ofnanoscale biostructures that may mimic the function of naturalbiosystems.

Nanotube probes or probe arrays with attached therapeutic moieties canalso be used in cell-based therapies to inject these therapeuticmoieties directly into cells where they are needed. Release of boundmoieties can be effected, for example, by a voltage pulse or other bonddestabilizing signal. The nanotube probes of the present invention canalso be employed to deliver genetic material (i.e., DNA) attached to theprobe tip to cells by similar injection techniques (e.g., duringembryonic development).

A nanotube mounted on a STM tip may also be used in desorption inducedby electronic transitions, or DIET. Field emitted electrons from the STMtip may be used to bring about hydrogen desorption, giving rise to usessuch as nanolithography and material modification on the nanometer andeven on the atomic scale.

A STM-tip attached nanotube may also be used in chemically-assistedfield evaporation/desorption (CAFE). The accuracy of the nanotubeprovides the ability to access a particular location on a surface, breakstrong chemical bonds, transfer one atom or cluster of atoms to thenanotube, and possibly redeposit the atom(s) at another location. Otherinteractions are also possible.

The nanotubes may also be used with scanned probe microscopy (SPM) tofabricate nanodevices. By attaching a nanotube to a tip of a SPM, ahighly localized enhanced oxidation of a substrate can be achieved, andthis may be used as an etch mark to create freestanding siliconnanowires. By further processing the nanowire, other confined structuresmay also be produced.

Manipulators, or “nanotools,” may be embodied by devices of the presentof invention. It is possible to create “nanoforcepts” which, throughmotion of one or more nanotube probe tips, can grip and move an objectof nanometer dimensions. Specific chemical derivitization of the probeend in this application can enhance, modify, or make chemically specificthe gripping action of the tip. Through electrical or electrochemicalaction, the tip can etch an object, moving atoms or molecules incontrolled patterns on a nanometer scale. Through catalytic cation of anindividual tip or catalytic action of chemical groups attached to thetip, one can achieve chemical modification of an object which can becarried out in a pattern which serves to fabricate patterns or othernanometer scale objects. Direct fabrication of individual structures onan atom-by-atom or molecule-by-molecule basis is possible using thenanoprobes disclosed in this invention. These nanotools may be used tomanipulate other nanoobjects, and may also be used to fabricate MEMS(Micro Electro Mechanical Systems).

The following sections provide more detail on the preparation of carbonnanotubes for use in the devices of the present invention.

Carbon Nanotubes

Fullerenes are molecules composed entirely of sp²-hybridized carbons,arranged in hexagons and pentagons. Fullerenes (e.g., C₆₀) were firstidentified as closed spheroidal cages produced by condensation fromvaporized carbon.

Fullerene tubes are produced in carbon deposits on the cathode in carbonarc methods of producing spheroidal fullerenes from vaporized carbon.Fullerene tubes may be closed at one or both ends with end caps or openat one or both ends. Ebbesen et al. (Ebbesen I), “Large-Scale SynthesisOf Carbon Nanotubes,” Nature, Vol. 358, p. 220 (Jul. 16, 1992) andEbbesen et al., (Ebbesen II), “Carbon Nanotubes,” Annual Review ofMaterials Science, Vol. 24, p. 235 (1994). Such tubes are referred toherein as carbon nanotubes. Many of the carbon nanotubes made by theseprocesses were multi-wall nanotubes, i.e., the carbon nanotubesresembled concentric cylinders. Carbon nanotubes having up to sevenwalls have been described in the prior art. Ebbesen II; Iijima et al.,“Helical Microtubules Of Graphitic Carbon,” Nature, Vol. 354, p. 56(Nov. 7, 1991).

Single-wall carbon nanotubes have been made in a DC arc dischargeapparatus of the type used in fullerene production by simultaneouslyevaporating carbon and a small percentage of Group VIII transition metalfrom the anode of the arc discharge apparatus. See Iijima et al.,“Single-Shell Carbon Nanotubes of 1 nm Diameter,” Nature, Vol. 363, p.603 (1993); Bethune et al., “Cobalt Catalyzed Growth of Carbon Nanotubeswith Single Atomic Layer Walls,” Nature, Vol. 63, p. 605 (1993); Ajayanet al., “Growth Morphologies During Cobalt Catalyzed Single-Shell CarbonNanotube Synthesis,” Chem. Phys. Lett., Vol. 215, p. 509 (1993); Zhou etal., “Single-Walled Carbon Nanotubes Growing Radially From YC₂Particles,” Appl. Phys. Lett., Vol. 65, p. 1593 (1994); Seraphin et al.,“Single-Walled Tubes and Encapsulation of Nanocrystals Into CarbonClusters,” Electrochem. Soc., Vol. 142, p. 290 (1995); Saito et al.,“Carbon Nanocapsules Encaging Metals and Carbides,” J. Phys. Chem.Solids, Vol. 54, p. 1849 (1993); Saito et al., “Extrusion of Single-WallCarbon Nanotubes Via Formation of Small Particles Condensed Near anEvaporation Source,” Chem. Phys. Lett, Vol. 236, p. 419 (1995). It isalso known that the use of mixtures of such transition metals cansignificantly enhance the yield of single-wall carbon nanotubes in thearc discharge apparatus. See Lambert et al., “Improving ConditionsToward Isolating Single-Shell Carbon Nanotubes,” Chem. Phys. Lett., Vol.226, p. 364 (1994).

An improved method of producing single-wall nanotubes is described inU.S. Ser. No. 08/687,665, entitled “Ropes of Single-Walled CarbonNanotubes” incorporated herein by reference in its entirety. This methoduses, inter alia, laser vaporization of a graphite substrate doped withtransition metal atoms, preferably nickel, cobalt, or a mixture thereof,to produce single-wall carbon nanotubes in yields of at least 50% of thecondensed carbon The single-wall nanotubes produced by this method tendto be formed in clusters, termed “ropes,” of 10 to 1000 single-wallcarbon nanotubes in parallel alignment, held together by van der Waalsforms in a triangular lattice.

The single-wall tubular fullerenes are distinguished from each other bydouble index (n,m) where n and m are integers that describe how to cut asingle strip of hexagonal “chicken-wire” graphite so that it makes thetube perfectly when it is wrapped onto the surface of a cylinder and theedges are sealed together. When the two indices are the same, m=n, theresultant tube is said to be of the “arm-chair” (or n,n) type, sincewhen the tube is cut perpendicular to the tube axis, only the sides ofthe hexagons are exposed and their pattern around the periphery of thetube edge resembles the arm and seat of an arm chair repeated n times.Arm-chair tubes are a preferred form of single-wall carbon nanotubessince they are metallic, and have extremely high electrical and thermalconductivity. In addition, all single-wall nanotubes have extremely hightensile strength.

Purification of Single-Wall Nanotubes

The product of a typical process for making mixtures containingsingle-wall carbon nanotubes is a tangled felt which can includedeposits of amorphous carbon, graphite, metal compounds (e.g., oxides),spherical fullerenes, catalyst particles (often coated with carbon orfullerenes) and possibly multi-wall carbon nanotubes. The single-wallcarbon nanotubes may be aggregated in “ropes” or bundles of essentiallyparallel nanotubes.

When material having a high proportion of single-wall nanotubes ispurified as described herein, the preparation produced will be enrichedin single-wall nanotubes, so that the single-wall nanotubes aresubstantially free of other material. In particular, single-wallnanotubes will make up at least 80% of the preparation, preferably atleast 90%, more preferably at least 95% and most preferably over 99% ofthe material in the purified preparation.

One preferred purification process comprises heating the SWNT-containingfelt under oxidizing conditions to remove the amorphous carbon depositsand other contaminating materials. In a preferred mode of thispurification procedure, the felt is heated in an aqueous solution of aninorganic oxidant, such as nitric acid, a mixture of hydrogen peroxideand sulfuric acid, or potassium permanganate. Preferably,SWNT-containing felts are refluxed in an aqueous solution of anoxidizing acid at a concentration high enough to etch away amorphouscarbon deposits within a practical time frame, but not so high that thesinge-wall carbon nanotube material will be etched to a significantdegree. Nitric acid at concentrations from 2.0 to 2.6 M have been foundto be suitable. At atmospheric pressure, the reflux temperature of suchan aqueous acid solution is about 101–102° C.

In a preferred process, the nanotube-containing felts can be refluxed ina nitric acid solution at a concentration of 2.6 M for 24 hours.Purified nanotubes may be recovered from the oxidizing acid byfiltration through, e.g., a 5 micron pore size TEFLON filter, likeMillipore Type LS. Preferably, a second 24 hour period of refluxing in afresh nitric solution of the same concentration is employed followed byfiltration as described above.

Refluxing under acidic oxidizing conditions may result in theesterification of some of the nanotubes, or nanotube contaminants. Thecontaminating ester material may be removed by saponification, forexample, by using a sodium hydroxide solution in ethanol at roomtemperature for 12 hours. Other conditions suitable for saponificationof any ester linked polymers produced in the oxidizing acid treatmentwill be readily apparent to those skilled in the art. Typically thenanotube preparation will be neutralized after the saponification step.Refluxing the nanotubes in 6M aqueous hydrochloric acid for 12 hours hasbeen found to be suitable for neutralization, although other suitableconditions will be apparent to the skilled artisan.

After oxidation, and optionally saponification and neutralization, thepurified nanotubes may be collected by settling or filtration preferablyin the form of a thin mat of purified fibers made of ropes or bundles ofSWNTs, referred to hereinafter as “bucky paper”. In a typical example,filtration of the purified and neutralized nanotubes on a TEFLONmembrane with 5 micron pore size produced a black mat of purifiednanotubes about 100 microns thick The nanotubes in the bucky paper maybe of varying lengths and may consists of individual nanotubes, orbundles or ropes of up to 10³ single-wall nanotubes, or mixtures ofindividual single-wall nanotubes and ropes of various thicknesses.Alternatively, bucky paper may be made up of nanotube which arehomogeneous in length or diameter and/or molecular structure due tofractionation as described hereinafter.

The purified nanotubes or bucky paper are finally dried, for example, bybaking at 850° C. in a hydrogen gas atmosphere, to produce dry, purifiednanotube preparations.

When laser-produced single-wall nanotube material, produced by thetwo-laser method of U.S. Ser. No. 08/687,665, was subjected refluxing in2.6 M aqueous nitric acid, with one solvent exchange, followed bysonication in saturated NaOH in ethanol at room temperature for 12hours, then neutralization by refluxing in 6M aqueous HCl for 12 hours,removal from the aqueous medium and baking in a hydrogen gas atmosphereat 850° C. in 1 atm H₂ gas (flowing at 1–10 sccm through a 1″ quartztube) for 2 hours, detailed TEM SEM and Raman spectral examinationshowed it to be >99% pure, with the dominant impurity being a fewcarbon-encapsulated Ni/Co particles. (See FIGS. 7A, 7B, and 7C).

In another embodiment, a slightly basic solution (e.g., pH ofapproximately 8–12) may also be used in the saponification step. Theinitial cleaning in 2.6 M HNO₃ converts amorphous carbon in the rawmaterial to various sizes of linked polycyclic compounds, such as fulvicand humic acids, as well as larger polycyclic aromatics with variousfunctional groups around the periphery, especially the carboxylic acidgroups. The base solution ionizes most of the polycyclic compounds,making them more soluble in aqueous solution. In a preferred process,the nanotube containing felts are refluxed in 2–5 M HNO₃ for 6-15 hoursat approximately 110°–125° C. Purified nanotubes may be filtered andwashed with 10 mM NaOH solution on a 3 micron pore size TSTP Isoporefilter. Next, the filtered nanotubes polished by stirring them for 30minutes at 60° C. in a S/N (Sulfuric acid/Nitric acid) solution In apreferred embodiment, this is a 3:1 by volume mixture of concentratedsulfuric acid and nitric acid. This step removes essentially all theremaining material from the tubes that is produced during the nitricacid treatment.

Once the polishing is complete, a four-fold dilution in water is made,and the nanotubes are again fileted on the 3 micron pore size TSTPIsopore filter. The nanotubes are again washed with a 10 mM NaOHsolution Finally, the nanotubes are stored in water, because drying thenanotubes makes it difficult to resuspend them.

Cutting Sine-Wall Carbon Nanotubes

Single-wall carbon nanotube produced by prior methods are so long andtangled that it is very difficult to purify them, or to manipulate them.They can be cut into short enough lengths that they are no longertangled and the open ends annealed closed. The short, closed tubularcarbon molecules may be purified and sorted very readily usingtechniques that are similar to those used to sort DNA or size polymers.

Preparation of homogeneous populations of short carbon nanotubesmolecules may be accomplished by cutting and annealing (reclosing) thenanotube pieces followed by fractionation. The cutting and annealingprocesses may be carried out on a purified nanotube bucky paper, onfelts prior to purification of nanotubes or on any material thatcontains single-wall nanotubes. When the cutting and annealing processis performed on felts, it is preferably followed by oxidativepurification, and optionally saponification, to remove amorphous carbon.Preferably, the starting material for the cutting process is purifiedsingle-wall nanotubes, substantially free of other material.

The short nanotube pieces can be cut to a length or selected from arange of lengths, that facilitates their intended use. The length can befrom just greater than the diameter of the tube up to about 1,000 timesthe diameter of the tube. Typical tubular molecules will be in the rangeof from about 5 to 1,000 nanometers or longer. For making templatearrays useful in growing carbon fibers of SWNT as described below,lengths of from about 50 to 500 nm are preferred.

Any method of cutting that achieves the desired length of nanotubemolecules without substantially affecting the structure of the remainingpieces can be employed. The preferred cutting method employs irradiationwith high mass ions. In this method, a sample is subjected to a fast ionbeam, e.g., from a cyclotron, at energies of from about 0.1 to 10giga-electron volts. Suitable high mass ions include those over about150 AMU's such as bismuth, gold, uranium and the like.

Preferably, populations of individual single-wall nanotube moleculeshaving homogeneous length are prepared starting with a heterogeneousbucky paper and cutting the nanotubes in the paper using a gold (Au⁺³³)fit ion beam. In a typical procedure, the bucky paper (about 100 micronthick) is exposed to ^(˜)10¹² fast ions per cm², which produces severelydamaged nanotubes in the paper, on average every 100 nanometers alongthe length of the nanotubes. The fast ions create damage to the buckypaper in a manner analogous to shooting 10–100 nm diameter “bulletholes” through the sample. The damaged nanotubes then can be annealed(closed) by heat sealing of the tubes at the point where ion damageoccurred, thus producing a multiplicity of shorter nanotube molecules.At these flux levels, the shorter tubular molecules produced will have arandom distribution of cut sizes with a length peak near about 100 nm.Suitable annealing conditions are well know in the fullerene art, suchas for example, baking the tubes in vacuum or inert gas at 1200° C. for1 hour.

The SWNTs may also be cut into shorter tubular molecules byintentionally incorporating defect-producing atoms into the structure ofthe SWNT during production. These defects can be exploited chemically(e.g., oxidatively attacked) to cut the SWNT into smaller pieces. Forexample, incorporation of 1 boron atom for every 1000 carbon atoms inthe original carbon vapor source can produce SWNTs with built-in weakspots for chemical attack.

Cutting may also be achieved by sonicating a suspension of SWNTs in asuitable medium such as liquid or molten hydrocarbons. One suchpreferred liquid is 1,2-dichloreothane. Any apparatus that producessuitable acoustic energy can be employed. One such apparatus is theCompact Cleaner (One Pint) manufactured by Cole-Parmer, Inc. This modeloperates at 40 KHZ and has an output of 20 W. The sonication cuttingprocess should be continued at a sufficient energy input and for asufficient time to substantially reduce the lengths of tubes, ropes orcables present in the original suspension. Typically times of from about10 minutes to about 24 hours can be employed depending on the nature ofthe starting material and degree of length reduction sought.

In another embodiment, sonification may be used to create defects alongthe rope lengths, either by the high temperatures and pressures createdin bubble collapse (−5000° C. and ˜1000 atm), or by the attack of freeradicals produced by sonochemistry. These defects are attacked by S/N tocleanly cut the nanotube, exposing the tubes underneath for more damageand cutting. In a preferred process, the nanotubes are bath sonocatedwhile being stirred in 40–45° C. S/N for 24 hours. Next, the nanotubesare stirred with no sonification in the S/N for 2 hours at 40–45° C.This is to attack, with the S/N, all the defects created by thesonification without creating more defects. Then, the nanotubes arediluted four-fold with water, and then filtered using a 0.1 micron poresize VCTP filter. Next, the nanotubes are filtered and washed with a 10mM NaOH solution on the VCTP filter. The nanotubes are polished bystirring them for 30 minutes at 70° C. in a S/N solution. The polishednanotubes are diluted four-fold with water, filtered using the 0.1micron pore size VCTP filters, then filtered and washed with 10 mM NaOHon a 0.1 micron pore size VCTP filter, and then stored in water.

Oxidative etching (e.g., with highly concentrated nitric acid) can alsobe employed to effect cutting of SWNTs into shorter lengths. Forexample, refluxing SWNT material in concentrated HNO₃ for periods ofseveral hours to 1 or 2 days will result in significantly shorter SWNTs.The rate of cutting by this mechanism is dependent on the degree ofhelicity of the tubes. This fact may be utilized to facilitateseparation of tubes by type, i.e., (n,n) from (m,n).

In another embodiment, SWNTs can be cut using electron beam cuttingapparatus in the known manner. Nanotubes may also be cut by the use of aplasma arc. Combination of the foregoing cutting techniques can also beemployed.

Homogeneous populations of single-walled nanotubes may be prepared byfractionating heterogeneous nanotube populations after annealing. Theannealed nanotubes may be disbursed in an aqueous detergent solution oran organic solvent for the fractionation. Preferably the tubes will bedisbursed by sonication in benzene, toluene, xylene or moltennaphthalene. The primary function of this procedure is to separatenanotubes that are held together in the form of ropes or mats by van derWaals force. Following separation into individual nanotubes, thenanotubes may be fractionated by size by using fractionation procedureswhich are well known, such as procedures for fractionating DNA orpolymer fractionation procedures. Fractionation also can be performed ontubes before annealing, particularly if the open ends have substituents(carboxy, hydroxy, etc.), that facilitate the fractionation either bysize or by type. Alternatively, the closed tubes can be opened andderivatized to provide such substituents. Closed tubes can also bederivatized to facilitate fractionation, for example, by addingsolubilizing moieties to the end caps.

Electrophoresis is one such technique well suited to fractionation ofSWNT molecules since they can easily be negatively charged. It is alsopossible to take advantage of the different polarization and electricalproperties of SWNTs having different structure types (e.g., arm chairand zig-zag) to separate the nanotubes by type. Separation by type canalso be facilitated by derivatizing the mixture of molecules with amoiety that preferentially bonds to one type of structure.

In a typical example, a 100 micron thick mat of black bucky paper, madeof nanotubes purified by refluxing in nitric acid for 48 hours wasexposed for 100 minutes to a 2 GeV beam of gold (Au⁺³³) ions in theTexas A&M Superconducting Cyclotron Facility (net flux of up to 10¹²ions per cm²). The irradiated paper was baked in a vacuum at 1200° C.for 1 hr to seal off the tubes at the “bullet holes”, and then dispersedin toluene while sonicating. The resultant tubular molecules wereexamined via SEM, AFM and TEM.

The procedures described herein produce tubular molecules that aresingle-wall nanotubes in which the cylindrical portion is formed from asubstantially defect-free sheet of graphene (carbon in the form ofattached hexagons) rolled up and joined at the two edges parallel to itslong axis. The nanotube can have a fullerene cap (e.g., hemispheric) atone end of the cylinder and a similar fullerene cap at the other end.One or both ends can also be open. Prepared as described herein, theseSWNT molecules are substantially free of amorphous carbon. Thesepurified nanotubes are effectively a whole new class of tubularmolecules.

In general the length, diameter and helicity of these molecules can becontrolled to any desired value. Preferred lengths are up to 10⁶hexagons; preferred diameters are about 5 to 50 hexagon circumference;and the preferred helical angle is 0° to 30°.

Preferably, the tubular molecules are produced by cutting and annealingnanotubes of predominantly arm-chair (n,n) configuration, which may beobtained by purifying material produced according to the methods of U.S.Ser. No. 08/687,665. These (n,n) carbon molecules, purified as describedherein, are the first truly “metallic molecules.” The metallic carbonmolecules are useful as probes for scanning probe microscopy such as areused in scanning tunneling microscopes (STM) and atomic forcemicroscopes (AFM).

Derivitization of Carbon Nanotubes

The tubular carbon molecules (including the multiwall forms) produced asdescribed above can be chemically derivatized at their ends (which maybe made either open or closed with a hemi-fullerene dome).Derivatization at the fullerene cap structures is facilitated by thewell-known reactivity of these structures. See, “The Chemistry ofFullerenes” R. Taylor ed., Vol. 4 of the advanced Series in Fullerenes,World Scientific Publishers, Singapore, 1995; A Hirsch, “The Chemistryof the Fullerenes,” Thieme, 1994. Alternatively, the fullerene caps ofthe single-walled nanotubes may be removed at one or both ends of thetubes by short exposure to oxidizing conditions (e.g., with nitric acidor O₂/CO₂) sufficient to open the tubes but not etch them back too for,and the resulting open tube ends maybe derivatized using known reactionschemes for the reactive sites at the graphene sheet edge.

In general the structure of such molecules can be shown as follows:

where

is a substantially defect-free cylindrical graphene sheet(whichoptionally can be doped with non-carbon atoms)having from about 10² toabout 10⁶ carbon atoms, andhaving a length of from about 5 to about 1000nm,preferably about 5 to about 500 nm;

is a fullerene cap that fits perfectly on the cylindricalgraphene sheet,has at least six pentagons and the remainderhexagons and typically hasat least about 30 carbon atoms;

-   -   n is a number from 0 to 30, preferably 0 to 12; and    -   R, R¹, R², R³, R⁴, and R⁵ each may be independently selected        from the group consisting of hydrogen; alkyl acyl, aryl aralkyl,        halogen; substituted or unsubstituted thiol; unsubstituted or        substituted amino; hydroxy, and OR′ wherein R′ is selected from        the group consisting of hydrogen, alkyl, acyl, aryl aralkyl,        unsubstituted or substituted amino; substituted or unsubstituted        thiol; and halogen; and a linear or cyclic carbon chain        optionally interrupted with one or more heteroatom, and        optionally substituted with one or more ═O, or ═S, hydroxy, an        aminoalkyl group, an amino acid, or a peptide of 2–8 amino        acids.

The following definitions are used herein.

The term “alkyl” as employed herein includes both straight and branchedchain radicals, for example methyl, ethyl, propyl, isopropyl, butyl,t-butyl, isobutyl, pentyl, hexyl, isohexyl, heptyl, 4,4-methylpentyl,octyl, 2,2,4-trimethylpentyl, nonyl, decyl, undecyl, dodecyl, thevarious branched chain isomers thereof. The chain may be linear orcyclic, saturated or unsaturated, containing, for example, double andtriple bonds. The alkyl chain may be interrupted or substituted with,for example, one or more halogen, oxygen, hydroxy, silyl, amino, orother acceptable substituents.

The term “acyl” as used herein refers to carbonyl groups of the formula—COR wherein R may be any suitable substituent such as, for example,alkyl, aryl, aralkyl, halogen; substituted or unsubstituted thiol;unsubstituted or substituted amino, unsubstituted or substituted oxygen,hydroxy, or hydrogen.

The term “aryl” as employed herein refers to monocyclic, bicyclic ortricyclic aromatic groups containing from 6 to 14 carbons in the ringportion, such as phenyl, naphthyl, substituted phenyl, or substitutednaphthyl, wherein the substituent on either the phenyl or naphthyl maybe for example C₁₋₄ alkyl, halogen, C₁₋₄ alkoxy, hydroxy or nitro.

The term “aralkyl” as used herein refers to alkyl groups as discussedabove having an aryl substituent, such as benzyl, p-nitrobenzyl,phenylethyl, diphenylmethyl, and triphenylmethyl.

The term “aromatic or non-aromatic ring” as used herein includes 5–8membered aromatic and non-aromatic rings uninterrupted or interruptedwith one or more heteroatom, for example O, S, SO, SO₂, and N, or thering may be unsubstituted or substituted with, for example, halogen,alkyl, acyl hydroxy, aryl, and amino, said heteroatom and substituentmay also be substituted with, for example, alkyl, acyl, aryl, oraralkyl.

The term “linear or cyclic” when used herein includes, for example, alinear chain which may optionally be interrupted by an aromatic ornon-aromatic ring. Cyclic chain includes, for example, an aromatic ornon-aromatic ring which may be connected to, for example, a carbon chainwhich either precedes or follows the ring.

The term “substituted amino” as used herein refers to an amino which maybe substituted with one or more substituent, for example, alkyl, acyl,aryl, aralkyl, hydroxy, and hydrogen.

The term “substituted thiol” as used herein refers to a thiol which maybe substituted with one or more substituent, for example, alkyl, acyl,aryl, aralkyl, hydroxy, and hydrogen.

Typically, open ends may contain up to about 20 substituents and closedends may contain up to about 30 substituents. It is preferred, due tostearic hindrance, to employ up to about 12 substituents per end.

In addition to the above described external derivatization, the SWNTmolecules of the present invention can be modified endohedrally, i.e.,by including one or more metal atoms inside the structure as is known inthe endohedral fullerene art. It is also possible to “load” the SWNTmolecule with one or more smaller molecules that do not bond to thestructures, e.g. C₆₀, to permit molecular switching as the C₆₀ buckyball shuttles back and forth inside the SWNT molecule under theinfluence of external fields or forces.

To produce endohedral tubular carbon molecules, the internal species(eg., meal atom, bucky ball molecules) can either be introduced duringthe SWNT formation process or added after preparation of the tubularmolecules. Incorporation of metals into the carbon source that isevaporated to form the SWNT material is accomplished in the mannerdescribed in the prior art for making endohedral metallofullerenes.Bucky balls, i.e., spheroidal fullerene molecules, are preferably loadedinto the tubular carbon molecules of this invention by removing one orboth end caps of the tubes employing oxidation etching described above,and adding an excess of bucky ball molecules (e.g., C₆₀, C₇₀) by heatingthe mixture (e.g., from about 500 to about 600° C.) in the presence ofC₆₀ or C₇₀ containing vapor for an equilibration period (e.g., fromabout 12 to about 36 hours). A significant proportion (e.g., from a fewtenths of a percent up to about 50 percent or more) of the tubes willcapture a bucky ball molecule during this treatment. By selecting therelative geometry of the tube and ball this process can be facilitated.For example, C₆₀ and C₇₀ fit very nicely in a tubular carbon moleculecut from a (10,10) SWNT (I.D.≡1 nm). After the loading step, the tubescontaining bucky ball molecules can be closed (annealed shut) by heatingunder vacuum to about 1100° C. Bucky ball encapsulation can be confirmedby microscopic examination, e.g., by TEM.

Endohedrally loaded tubular carbon molecules can then be separated fromempty tubes and any remaining loading materials by taking advantage ofthe new properties introduced into the loaded tubular molecules, forexample, where the metal atom imparts magnetic or paramagneticproperties to the tube, or the bucky ball imparts extra mass to thetubes. Separation and purification methods based on these properties andothers will be readily apparent to those skilled in the art.

Fullerene molecules like C₆₀ or C₇₀ will remain inside the properlyselected tubular molecule (e.g., one based on (10,10) SWNTs) becausefrom an electronic standpoint (e.g., by van der Waals interaction) thetube provides an environment with a more stable energy configurationthan that available outside the tube.

Molecular Arrays of Single-Wall Carbon Nanotubes

An application of particular interest for a homogeneous population ofSWNT molecules is production of a substantially two-dimensional arraymade up of single-walled nanotubes aggregating (e.g., by van der Waalsforces) in substantially parallel orientation to form a monolayerextending in directions substantially perpendicular to the orientationof the individual nanotubes. Such monolayer arrays can be formed byconventional techniques employing “self-assembled monolayers” (SAM) orLangmiur-Blodgett films, see Hirch, pp. 75–76. Such a molecular array isillustrated schematically in FIG. 8. In this Figure nanotubes 802 arebound to a substrate 804 having a reactive coating 806 (e.g., gold).

Typically, SAMs are created on a substrate which can be a metal (such asgold, mercury or ITO (indium-tin-oxide)). The molecules of interest,here the SWNT molecules, are linked (usually covalently) to thesubstrate through a linker moiety such as —S—, —S—(CH₂)_(n)—NH—,—SiO₃(CH₂)₃NH— or the like. The linker moiety may be bound first to thesubstrate layer or first to the SWNT molecule (at an open or closed end)to provide for reactive self-assembly. Langmiur-Blodgett films areformed at the interface between two phases, e.g., a hydrocarbon (e.g.,benzene or toluene) and water. Orientation in the film is achieved byemploying molecules or linkers that have hydrophilic and lipophilicmoieties at opposite ends.

The configuration of the SWNT molecular array may be homogeneous orheterogeneous depending on the use to which it will be put. Using SWNTmolecules of the same type and structure provides a homogeneous array ofthe type shown in FIG. 8. By using different SWNT molecules, either arandom or ordered heterogeneous structure can be produced. An example ofan ordered heterogeneous array is shown in FIG. 9 where tubes 902 are(n,n), i.e., metallic in structure and tubes 904 are (m,n), i.e.,insulating. This configuration can be achieved by employing successivereactions after removal of previously masked areas of the reactivesubstrate.

One preferred use of the SWNT molecular arrays of the present inventionis to provide a “seed” or template for growth of carbon fiber ofsingle-wall carbon nanotubes as described below. The use of thistemplate is particularly useful for keeping the live (open) end of thenanotubes exposed to feedstock during growth of the fiber. The templatearray of this invention can be used as formed on the original substrate,cleaved from its original substrate and used with no substrate (the vander Waals forces will hold it together) or transferred to a secondsubstrate more suitable for the conditions of fiber growth.

Where the SWNT molecular array is to be used as a seed or template forgrowing macroscopic carbon fiber as described below, the array need notbe formed as a substantially two-dimensional array. Any form of arraythat presents at its upper surface a two-dimensional array can beemployed. In the preferred embodiment, the template molecular array is amanipulatable length of carbon fiber as produced below.

Another method for forming a suitable template molecular array involvesemploying purified bucky paper as the starting material. Upon oxidativetreatment of the bucky paper surface (e.g., with O₂/CO₂ at about 500°C.), the sides as well as ends of SWNTs are attacked and many tubeand/or rope ends protrude up from the surface of the paper. Disposingthe resulting bucky paper in an electric field (e.g., 100 V/cm² resultsin the protruding tubes and or ropes aligning in a directionsubstantially perpendicular to the paper surface. These tubes tend tocoalesce due to van der Waals forces to form a molecular array.

Alternatively, a molecular array of SWNTs can be made by “combing” thepurified bucky paper starting material. “Combing” involves the use of asharp microscopic tip such as the silicon pyramid on the cantilever of ascanning force microscope (“SFM”) to align the nanotubes. Specifically,combing is the process whereby the tip of an SFM is systematicallydipped into, dragged through, and raised up from a section of buckypaper. An entire segment of bucky paper could be comb, for example, by:(i) systematically dipping, dragging, raising and moving forward an SFMtip along a section of the bucky paper, (ii) repeating the sequence in(i) until completion of a row; and (iii) repositioning the tip alonganother row and repeating (i) and (ii). In a preferred method ofcombing, the section of bucky paper of interest is combed through as insteps (i)–(iii) above at a certain depth and then the entire process isrepeated at another depth. For example, a lithography script can bewritten and run which could draw twenty lines with 0.5 μm spacing in a10×10 μm square of bucky paper. The script can be run seven times,changing the depth from zero to three μm in 0.5 μm increments.

Growth of Carbon Fiber from SWNT Molecular Arrays

The present invention provides methods for growing carbon fiber fromSWNT molecular arrays to any desired length. The carbon fiber whichcomprises an aggregation of substantially parallel carbon nanotubes maybe produced according to this invention by growth (elongation) of asuitable seed molecular array. The preferred SWNT molecular array isproduced as described above from a SAM of SWNT molecules ofsubstantially uniform length. The diameter of the fibers grown accordingto this method, which are useful in making nanoscale probes andmanipulators, can be any value from a few (<10) nanotubes to ropes up to10³ nanotubes.

The first step in the growth process is to open the growth end of theSWNTs in the molecular array. This can be accomplished as describedabove with an oxidative treatment. Next, a transition metal catalyst isadded to the open-ended seed array. The transition metal catalyst can beany transition metal that will cause conversion of the carbon-containingfeedstock described below into highly mobile carbon radicals that canrearrange at the growing edge to the favored hexagon structure. Suitablematerials include transition metals, and particularly the Group VIIItransition metals i.e., iron (Fe), cobalt (Co), nicked (NI), ruthenium(Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir) andplatinum (Pt). Metals from the lanthanide and actinide series andmolybdenum can also be used. Preferred are Fe, Ni, Co and mixturesthereof. Most preferred is a 50/50 mixture (by weight) of Ni and Co.

The catalyst should be present on the open SWNT ends as a metal clustercontaining from about 10 metal atoms up to about 200 metal atoms(depending on the SWNT molecule diameter). Typically, the reactionproceeds most efficiently if the catalyst metal cluster sits on top ofthe open tube and does not bridge over more than one or two tubes.Preferred are metal clusters having a cross-section equal to from about0.5 to about 1.0 times the tube diameter (e.g., about 0.7 to 1.5 nm).

In the preferred process, the catalyst is formed, in situ, on the opentube ends of the molecular array by a vacuum deposition process. Anysuitable equipment, such as that used in Molecular Beam Epitaxy (MBE)deposition, can be employed. One such device is a Küdsen Effusion SourceEvaporator. It is also possible to effect sufficient deposition of metalby simply heating a wire in the vicinity of the tube ends (e.g., a Ni/COwire or separate Ni and CO wires) to a temperature below the meltingpoint at which enough atoms evaporate from one wire sure (e.g., fromabout 900 to about 1300° C.). The deposition is preferably carried outin a vacuum with prior outgassing. Vacuums of about 10⁻⁶ to 10⁻⁸ Torrare stable. The evaporation temperature should be high enough toevaporate the metal catalyst. Typically, temperatures in the range of1500 to 2000° C. are suitable for the Ni/Co catalyst of the preferredembodiment. In the evaporation process, the metal is typically depositedas monolayers of metal atoms. From about 1–10 monolayers will generallygive the required amount of catalyst. The deposition of transition metalclusters on the open tube tops can also be accomplished by laservaporization of metal targets in a catalyst deposition zone.

The actual catalyst metal cluster formation at the open tube ends iscarried out by heating the tube ends to a temperature high enough toprovide sufficient species mobility to permit the metal atoms to findthe open ends and assemble into clusters, but not so high as to effectclosure of the tube ends. Typically, temperatures of up to about 500° C.are suitable. Temperatures in the range of about 400–500° C. arepreferred for the Ni/Co catalysts system of one preferred embodiment.

In a preferred embodiment, the catalyst metal cluster is deposited onthe open nanotube end by a docking process that insures optimum locationfor the subsequent growth reaction. In this process, the metal atoms aresupplied as described above, but the conditions are modified to providereductive conditions, e.g., at 800° C., 10 millitorr of H₂ for 1 to 10minutes. There conditions cause the metal atom clusters to migratethrough the system in search of a reactive site. During the reductiveheating the catalyst material will ultimately find and settle on theopen tube ends and begin to etch back the tube. The reduction periodshould be long enough for the catalyst particles to find and begin toetch back the nanotubes, but not so long as to substantially etch awaythe tubes. By changing to the above-described growth conditions, theetch-back process is reversed. At this point, the catalyst particles areoptimally located with respect to the tube ends since they already werecatalytically active at those sites (albeit in the reverse process).

The catalyst can also be supplied in the form of catalyst precursorswhich convert to active form under growth conditions such as oxides,other salts or ligand stabilized metal complexes. As an example,transition metal complexes with alkylamines (primary, secondary ortertiary) can be employed. Similar alkylamine complexes of transitionmetal oxides also can be employed.

In an alternative embodiment, the catalyst may be supplied as preformednanoparticles (i.e., a few nanometers in diameter) as described in Daiet al., “Single-Wall Nanotubes Produced by Metal-CatalyzedDisproportionation of Carbon Monoxide,” Chem. Phys. Lett. 260 (1996),471–475.

In the next step of the process, the SWNT molecular array with catalystdeposited on the open tube ends is subjected to tube growth (extension)conditions. This may be in the same apparatus in which the catalyst isdeposited or a different apparatus. The apparatus for carrying out thisprocess will require, at a minimum, a source of carbon-containingfeedstock and a means for maintaining the growing end of the continuousfiber at a growth and annealing temperature where carbon from the vaporcan be added to the growing ends of the individual nanotubes under thedirection of the transition metal catalyst. Typically, the apparatuswill also have means for continuously collecting the carbon fiber. Theprocess will be described for illustration purposes with reference tothe apparatus shown in FIGS. 10 and 11.

The carbon supply necessary to grow the SWNT molecular array into acontinuous fiber is supplied to the reactor 1000, in gaseous formthrough inlet 1002. The gas stream should be directed towards the frontsurface of the growing array 1004. The gaseous carbon-containingfeedstock can be any hydrocarbon or mixture of hydrocarbons includingalkyls, acyls, aryls, aralkyls and the like, as defined above. Preferredare hydrocarbons having from about 1 to 7 carbon atoms. Particularlypreferred are methane, ethane, ethylene, actylene, acetone, propane,propylene and the like. Most preferred is ethylene. Carbon monoxide mayalso be used and in some reactions is preferred. Use of CO feedstockwith preformed Mo-based nano-catalyst is believed to follow a differentreaction mechanism than that proposed for in situ-formed catalystclusters. See Dai.

The feedsock concentration is preferably as chosen to maximize the rateof reaction, with higher concentrations of hydrocarbon giving fastergrowth rates. In general, the partial pressure of the feedstock material(e.g., ethylene) can be in the 0.001 to 10.0 Torr range, with values inthe range of about 1.0 to 10 Torr being preferred. The growth rate isalso a function of the temperature of the growing array tip as describedbelow, and as a result growth temperatures and feed stock concentrationcan be balanced to provide the desired growth rates.

It is not necessary or preferred to preheat the carbon feedstock gas,since unwanted pyrolysis at the reactor walls can be minimized thereby.The only heat supplied for the growth reaction should be focused at thegrowing tip of the fiber 1004. The rest of the fiber and the reactionapparatus can be kept at room temperature. Heat can be supplied in alocalized fashion by any suitable means. For the small fibers useful inmaking nanoscale probes and manipulators, a laser 1006 focused at thegrowing end is pored (eg., a C-W laser such as an argon ion laser beamat 514 nm). For larger fibers, heat can be supplied by microwave energyor R-F energy, again localized at the growing fiber tip. Any other formof concentrated electromagnetic energy that can be focused on thegrowing tip can be employed (e.g., solar energy). Care should be taken,however, to avoid electromagnetic radiation that will be absorbed to anyappreciable extent by the feedstock gas.

The SWNT molecular array tip should be heated to a temperaturesufficient to cause growth and efficient annealing of defects in thegrowing fiber, thus forming a growth and annealing zone at the tip. Ingeneral, the upper limit of this temperature is governed by the need toavoid pyrolysis of the feedstock and fouling of the reactor orevaporation of the deposited metal catalyst. For most feedstocks, thisis below about 1300° C. The lower end of the acceptable temperaturerange is typically about 500° C., depending on the feedstock andcatalyst efficiency. Preferred are temperatures in the range of about500° C. to about 1200° C. More preferred are temperatures in the rangeof from about 700° C. to about 1200° C. Temperatures in the range ofabout 900° C. to about 1100° C. are the most preferred, since at thesetemperatures the best annealing of defects occurs. The temperature atthe growing end of the cable is preferably monitored by, and controlledin response to, an optical pyrometer 1008, which measures theincandescence produced. While not preferred due to potential foulingproblems, it is possible under some circumstances to employ an inertsweep gas such as argon or helium.

In general, pressure in the growth chamber can be in the range of 1millitorr to about 1 atmosphere. The total pressure should be kept at 1to 2 times the partial pressure of the carbon feedstock. A vacuum pump1010 may be provided as shown. It may be desirable to recycle thefeedstock mixture to the growth chamber. As the fiber grows it can bewithdrawn from the growth chamber 1012 by a suitable transport mechanismsuch as drive roll 1014 and idler roll 1016. The growth chamber 1012 isin direct communication with a vacuum feed lock zone.

The pressure in the growth chamber can be brought up to atmospheric, ifnecessary, in the vacuum feed lock by using a series of chambers 1100.Each of these chambers is separated by a loose TEFLON O-ring seal 1102surrounding the moving fiber. Pumps 1104 effect the differentialpressure equalization. A take-up roll 1106 continuously collects theroom temperature carbon fiber cable. Product output of this process canbe in the range of 10⁻³ to 10¹ feet per minute or more. By this process,it is possible to produce tons per day of continuous carbon fiber madeup of SWNT molecules.

Growth of the fiber can be terminated at any stage (either to facilitatemanufacture of a fiber of a particular length or when too many defectsoccur). To restart growth, the end may be cleaned (i.e., reopened) byoxidative etching (chemically or electrochemically). The catalystparticles can then be reformed on the open tube ends, and growthcontinued.

The molecular array (template) may be removed from the fiber before orafter growth by macroscopic physical separation means, for example bycutting the fiber with scissors to the desired length. Any section fromthe fiber may be used as the template to initiate production of similarfibers.

The continuous carbon fiber of the present invention can also be grownfrom more than one separately prepared molecular array or template. Themultiple arrays can be the same or different with respect to the SWNTtype or geometric arrangement in the array. Cable-like structures withenhanced tensile properties can be grown from a number of smallerseparate arrays as shown in FIG. 12. In addition to the masking andcoating techniques described above, it is possible to prepare acomposite structure, for example, by surrounding a central core army ofmetallic SWNTs with a series of smaller circular non-metallic SWNTarrays arranged in a ring around the core array as shown in FIG. 13.

The carbon nanotube structures useful according to this invention neednot be round or even symmetrical in two-dimensional cross section. It iseven possible to align multiple molecular array seed templates in amanner as to induce nonparallel growth of SWNTs in some portions of thecomposite fiber, thus producing a twisted, helical rope, for example. Itis also possible to catalytically grow carbon fiber in the presence ofan electric field to aid in alignment of the SWNTs in the fibers, asdescribed above in connection with the formation of template arrays.

Random Growth of Carbon Fibers From SWNTs

It is also possible to produce useful compositions comprising a randomlyoriented mass of SWNTs, which can include individual tubes, ropes and/orcables. The random growth process has the ability to produce largequantities, i.e., tons per day, of SWNT material.

In general the random growth method comprises providing a plurality ofSWNT seed molecules that are supplied with a suitable transition metalcatalyst as described above, and subjecting the seed molecules to SWNTgrowth conditions that result in elongation of the seed molecule byseveral orders of magnitude, e.g., 10² to 10¹⁰ or more times itsoriginal length.

The seed SWNT molecules can be produced as described above, preferablyin relatively short lengths, e.g., by cutting a continuous fiber orpurified bucky paper. In a preferred embodiment, the seed molecules canbe obtained after one initial run from the SWNT felt produced by thisrandom growth process (e.g., by cutting). The lengths do not need to beuniform and generally can range from about 5 nm to 10 μm in length.

These SWNT seed molecules may be formed on nanoscale supports that donot participate in the growth reaction. In another embodiment, SWNTs orSWNT structures can be employed as the support material/seed. Forexample, the self assembling technique described below can be used toform a three-dimensional SWNT nanostructure. Nanoscale powders producedby these technique have the adavantage that at the support material canparticipate in the random growth process.

The supported or unsupported SWNT seed materials can be combined with asuitable growth catalyst as described above, by opening SWNT moleculeends and depositing a metal atom cluster. Alternatively, the growthcatalyst can be provided to the open end or ends of the seed moleculesby evaporating a suspension of the seeds in a suitable liquid containinga soluble or suspended catalyst precursor. For example, when the liquidis water, soluble metal salts such as Fe(NO₃)₃, Ni(NO₃)₂ or CO (NO₃)₂and the like may be employed as catalyst precursors. In order to ensurethat the catalyst material is properly positioned on the open end(s) ofthe SWNT seed molecules, it may be necessary in some circumstances toderivitize the SWNT ends with a moiety that binds the catalystnanoparticle or more preferably a ligand-stabilized catalystnanoparticle.

In the first step of the random growth process the suspension of seedparticles containing attached catalysts or associated with dissolvedcatalyst precursors is injected into an evaporation zone where themixture contacts a sweep gas flow and is heated to a temperature in therange of 250–500° C. to flash evaporate the liquid and provide anentrained reactive nanoparticle (i.e., seed/catalyst). Optionally thisentrained particle stream is subjected to a reduction step to furtheractivate the catalyst (e.g., heating from 300–500° C. in H₂). Acarbonaceous feedstock gas, of the type employed in the continuousgrowth method described above, is then introduced into the sweepgas/active nanoparticle stream and the mixture is carried by the sweepgas into and through a growth zone.

The reaction conditions for the growth zone are as described above,i.e., 500–1000° C. and a total pressure of about one atmosphere. Thepartial pressure of the feedstock gas (e.g., ethylene, CO) can be in therange of about 1 to 100 Torr. The reaction is preferably carried out ina tubular reactor through which a sweep gas (e.g., argon) flows.

The growth zone may be maintained at the appropriate growth temperatureby 1) preheating the feedstock gas, 2) preheating the sweep gas, 3)externally heating the growth zone, 4) applying localized heating in thegrowth zone, e.g., by laser or induction coil, or any combination of theforegoing.

Downstream recovery of the product produced by this process can beeffected by known means such as filtration, centrifugation the like.Purification may be accomplished as described above.

The carbon nanotubes prepared by the above described process may alsoemploy the hexaboronitride lattice. This material forms graphene-likesheets with the hexagons made of B and N atoms (e.g., B₃ N₂ or C₂ BN₃).It is possible to provide an outer coating to a growing carbon fiber bysupplying a BN precursor (eg., tri-chloroborazine, a mixture of NH₃ andBCl₃ or diborane) to the fiber which serves as a mandrel for thedeposition of BN sheets. This outer BN layer can provide enhancedinsulating properties to the metallic carbon fiber of the presentinvention. Outer layers of pyrolytic carbon polymers or polymer blendsmay also be employed to impart insulating properties. By changing thefeedstock in the above described process from a hydrocarbon to a BNprecursor and back again it is possible to grow a fiber made up ofindividual tubes that alternate between regions of all carbon latticeand regions of BN lattice. In another embodiment, an all BN fiber can begrown by starting with a SWNT template array topped with a suitablecatalyst and fed BN precursors. These graphene and BN systems can bemixed because of the very close match of size to the two hexagonal unitsof structure. In addition, they exhibit enhanced properties due to theclose match of coefficients of thermal expansion and tensile properties.

While the invention has been particularly shown and described by theforegoing detailed description, it will be understood by those skilledin the art that various other changes in form and detail may be madewithout departing from the spirit and scope of the invention.

1. A method for purifying single-wall carbon nanotubes comprising: a)providing a mixture containing single-wall carbon nanotubes and at leastone other reaction product formed in a method for producing single-wallcarbon nanotubes; b) heating the mixture under oxidizing conditions; andc) recovering a purified product having a higher concentration of singlewall carbon nanotubes than the mixture.
 2. The method of claim 1 whereinthe oxidizing conditions provide for derivitization of at least one ofthe single-wall carbon nanotubes.
 3. The method of claim 1 wherein theoxidizing conditions provide for esterification of at least one of thesingle-wall carbon nanotubes.
 4. The method of claim 1 furthercomprising reacting at least a portion of the at least one otherreaction product to form a compound, wherein the compound is capable ofbeing dissolved or suspended in an aqueous solution.
 5. The method ofclaim 1 wherein the purified product is suspended in a liquid.
 6. Themethod of claim 1 wherein the purified product is a solid product. 7.The method of claim 6 wherein the solid product is recovered by a methodselected from the group consisting of settling, filtration andcombinations thereof.
 8. The method of claim 1 further comprisingstoring the purified product in water.
 9. The method of claim 6 whereinthe solid product comprises a mat.
 10. The method of claim 9 wherein themat comprises at least one material selected from the group consistingof ropes of single-wall carbon nanotubes, bundles of single-wall carbonnanotubes and combinations thereof.
 11. The method of claim 1 furthercomprising drying the purified product.
 12. The method of claim 11wherein the drying is at about 850° C. in a hydrogen gas atmosphere. 13.The method of claim 5 wherein the purified product suspended in theliquid comprises at least 80% by weight single-wall carbon nanotubes.14. The method of claim 5 wherein the purified product suspended in theliquid comprises at least 90% by weight single-wall carbon nanotubes.15. The method of claim 5 wherein the purified product suspended in theliquid comprises at least 95% by weight single-wall carbon nanotubes.16. The method of claim 5 wherein the purified product suspended in theliquid comprises at least 99% by weight single-wall carbon nanotubes.17. The method of claim 6 wherein the solid product comprises at least80% by weight single-wall carbon nanotubes.
 18. The method of claim 6wherein the solid product comprises at least 90% by weight single-wallcarbon nanotubes.
 19. The method of claim 6 wherein the solid productcomprises at least 95% by weight single-wall carbon nanotubes.
 20. Themethod of claim 6 wherein the solid product comprises at least 99% byweight single-wall carbon nanotubes.
 21. A method for purifyingsingle-wall carbon nanotubes comprising: a) providing a mixturecomprising single-wall carbon nanotubes, an amorphous carbon deposit andat least one other reaction product; b) heating the mixture underoxidizing conditions sufficient to oxidize the amorphous carbon and theat least one other reaction product; and c) recovering a purifiedproduct that comprises at least 80% by weight single-wall carbonnanotubes.
 22. The method of claim 21 wherein the oxidizing conditionsare sufficient to remove at least a portion of the amorphous carbondeposit and at least portion of the at least one other reaction product.23. The method of claim 21 wherein the purified product is recovered bya method selected from the group consisting of settling, filtration anda combination thereof.
 24. The method of claim 21 wherein the oxidizingconditions comprise heating the mixture in an aqueous solution of aninorganic oxidant.
 25. The method of claim 24 wherein the aqueoussolution is heated to reflux.
 26. The method of claim 23 wherein theinorganic oxidant comprises a chemical selected from the groupconsisting of nitric acid, sulfuric acid, hydrogen peroxide, potassiumpermanganate and mixtures thereof.
 27. The method of claim 23 whereinthe aqueous solution comprises nitric acid at a concentration between2.0 and 2.6 Molar.
 28. The method of claim 21 further comprisingremoving at least one esterified amorphous carbon deposit, wherein theat least one esterified amorphous carbon deposit is formed under theoxidizing conditions.
 29. The method of claim 21 further comprising asaponification treatment of the mixture.
 30. The method of claim 29wherein the saponification treatment comprises contacting the amorphouscarbon deposit with a basic solution.
 31. The method of claim 29 whereinthe saponification treatment further comprises sonication.
 32. Themethod of a claim 30 wherein the basic solution comprises sodiumhydroxide.
 33. The method of claim 29 comprising neutralizing themixture with an acid.
 34. The method of claim 33 wherein the acid isselected from the group consisting of hydrochloric acid, sulfuric acid,nitric acid and mixtures thereof.
 35. A method for purifying a mixturecomprising single-wall carbon nanotubes and amorphous carboncontaminate, the method comprising the steps of: (a) heating the mixtureunder oxidizing conditions sufficient to remove the amorphous carbon;and (b) recovering a product comprising at least about 80% by weight ofsingle-wall carbon nanotubes.
 36. The method of claim 35 wherein theproduct recovered is baked in hydrogen gas.